Salt-like reaction products of hals derivatives and phosphor-cntaining organic acids for the stabilisation of polymeric materials

ABSTRACT

This invention relates to salt reaction products resp. premanufactured mixtures of compounds, which contain one or more groups of formula (Ia) to (Ic),  
                 
 
reaction products of  
                 
 
and organophosphorus acids resp. their derivatives, which contain one or more groups of formula (II),  
                 
wherin the symbols have the meanings as given in claim 1 of the application. The invention further relates to a process for the preparation of saltlike reaction products and premanufactured mixtures. The saltlike reaction products and premanufactured mixtures can be used for stabilisation of polymers, in particularly polar polymers such as polyamides and polyesters, and for the improvement of the processing properties, heat stability, colour, gloss, surface and mechanical properties of these polymers.

The present invention relates to new saltlike reaction productsrespectively premanufactured mixtures of compounds selected from thegroup of sterically hindered amine light stabilisers (HALS compounds)with organophosphorus acids or organophosphorus acid derivatives(organophosphorus acids and derivatives are in the following togethercalled “organo P-acids”).

The saltlike products respectively mixtures are suitable for the heatand/or light stabilisation of polymer materials and are also suitablefor the improvement of the processing and long term stability ofpolymers.

As known to the person skilled in the art, the stabilizing effect ofHALS-compounds during exposition to mineral acids, for exampleoriginating from acid rain or from decomposition products of biocides orflame retardants, is dramatically reduced. This is considered to bemainly due to the formation of saltlike products of the HALS-compoundswith mineral acids.

Surprisingly, it has now been found, that the products of the invention,although they have a saltlike character, are suitable for thestabilisation of polymers, in particular for the stabilisation of polarpolymers, such as polyamide or polyester. Moreover, the products of theinvention provide for an improvement of the processing properties, suchas flowability during extrusion, injection molding or fiber spinning,for an improvement of colour, gloss, surface quality and/or themechanical properties of the final product.

The HALS-compounds (I) are selected from the following general formulae(Ia) to (Ic):

reaction products of

wherein the residues independently are selected from

-   -   A is —O— or —NR′—,    -   R′ is H, C₁-C₁₈-alkyl or a group selected from        with    -   R″ H, C₁-C₁₈-alkyl,    -   R′″ H, an aliphatic, cycloaliphatic, aromatic or heteroaromatic        residue,    -   R₁ is C₁-C₁₈-alkyl, or two groups R₁ bound to the same carbon        form a C₄-C₈-cycloalkyl residue,    -   R₂ is H or C₁-C₁₈-alkyl, C₇-C₁₈-alkylaryl,    -   R₃ is H, or a n-valent aliphatic, cycloaliphatic, aromatic or        heteroaromatic residue,    -   R₄ is C₁-C₁₈-alkyl, —C(O)—C₁-C₁₈-alkyl or —C₁-C₈-alkyl        —C(O)O—C₁-C₁₈-alkyl;    -   R₅ is H, C₁-C₁₈-alkyl, C₄-C₁₈-cycloalkyl or two groups R₅ bound        to the same carbon form a C₄-C₁₈-cycloalkyl residue and    -   n a whole number >0.

The organo P-acids mentioned above are characterised by the generalformula (II):

in which

-   -   independently of each other    -   R₇ is H, a m-valent aliphatic, cycloaliphatic, aromatic or        heteroaromatic residue or —OR₉;    -   R₈ is H, an aliphatic, cycloaliphatic, aromatic or        heteroaromatic residue or —OR₉;    -   R₉ is H, an aliphatic, cycloaliphatic, aromatic or        heteroaromatic residue,    -   m is a whole number >0, preferably m is 1, 2, 3 or 4; more        preferably 1 or 2.

The preferred groups R₁ are methyl. Also preferred are two groups R₁bound to the same carbon atom forming a C₄-C₆-cycloalkyl ring.

Preferred groups R₂ are H, C₁-C₁₂-alkyl or benzyl.

Preferred groups R₃ are represented by the following residues

-   -   R₃ C₁-C₁₈-alkyl, C₁-C₁₈-alkylene, C₅-C₁₂-cycloalkyl,        C₅-C₁₂-cycloalkylene, C₆-C₁₈-aryl, C₆-C₁₈-arylene,        C₅-C₁₈-heteroaryl, C₅-C₁₈-heteroarylene, C₆-C₃₆-arylalkyl,        C₆-C₃₆-arylalkylene, C₆-C₃₆-alkylaryl,C₆-C₃₆-alkylarylene and        the residue        where p represents a whole number between 1-4.

Preferred groups R₇ , R₈ , R₉ are C₁-C₁₈-alkyl, C₁-C₁₈-alkylene,C₅-C₁₂-cycloalkyl, C₅-C₁₂-cycloalkylene, C₆-C₁₈-aryl, C₆-C₁₈-arylene,C₅-C₁₈-heteroaryl, C₅-C₁₈-heteroarylene, C₆-C₃₆-arylalkyl,C₆-C₃₆-arylalkylene, C₆-C₃₆-alkylaryl,C₆-C₃₆-alkylarylene.

Preferred embodiments of the invention are saltlike compounds (III) withthe general formulae (IIIa) to (IIIc)

wherein n and m are greater than zero and the other substituents aredefined as above.

Compounds of formulae (IIa) to (IIIc) comprising polyvalent substituentsR₃ or R₇, may optionally comprise further groups of formula (I a) and/or(II).

Formula (IV) represents a particularly preferred candidate of thecompound (III)

in which

-   -   r is a whole number between 0 and 3,    -   s represents (r+1)/m and    -   the other residues have the meanings given above,

Formula (V) represents the most preferred candidate of the compound(III)

wherein r is 1 and

-   -   wherein the residues are the same as described above.

The products of the invention can be prepared in a reaction of one ormore HALS-compounds (I) with one or more organo P-acids (II), where,depending on the molar ratio of the reaction partners and the reactionconditions, full- or hemi-amine salts of organo P-acids are formed.These salts show to some extent a considerably higher solubility inwater or lower alcohols.

The products of the invention can be synthesised in solvents,preferrably in water or lower alcohols, or they can be synthesised inthe melt. The obtained solutions can either be used directly or theproducts can be isolated by removal of the solvent. The resulting solidscan be used in a subsequent process, optionally after further finishing.

The application of the products of the invention in polycondensationpolymers like polyamide 6.6, PET or similar types, which are producedfrom a di-acid and a di-amino- or a diol component respectively, areparticularly advantageous, as the products of the invention are easilyand homogeneously dispersed in the reaction mixture during thepolycondensation reaction due to their good solubility. TheHALS-compounds themselves on the other hand are less soluble due totheir hydrophobic character and therefore are more difficult to behomogeneously dispersed.

Other members of the group of products of the invention are bettersuited for the use in polymer melt processing due to their lowerpolarity. It was found that the preferred properties can be influencedby the selection of the components (I) and (II) within a wide range.

A further object of the invention are premanufactured mixtures ofcompounds—so-called “blends” in the plastic industry—consisting of thecomponents (I) and (II) in a selected molar ratio. The products of theinvention according to formula (III) can thereby be partly or completelyformed already during the making of such blends, or during incorporationinto the polymer mass, respectively during incorporation into the rawmaterials. The latter can be for example ε-Caprolactam (for PA6),AH-Salt-solution (for PA6.6) or precondensates from di-acids and dioles(for polyester).

As already known to the skilled person, such saltlike productsrespectively mixtures can also be formed by the use of HALS-compoundsduring the polycondensation and may disappear during continuedpolycondensation.

The premanufactured mixtures (blends) of the present invention are welldefined with selected molar ratios. They are prepared by technicalprocesses applicable also on large scale, which depending on thereaction conditions, already may partly form compounds of formula (III).Such blends, containing the appropriate amounts of component (I) and(II), may be added to the polycondensate. These premanufactured mixturescan be obtained from the melt (drop granulation techniques, prilling,extrusion, etc.), by compacting (roller compactors, tabletting,briquetting, press granulation, etc.), by granulation processes(spraying, fluidized bed granulation, drum granulation, etc.) or just bysimple mixing.

The HALS-compounds, as well as the organo P-acids, can be mono- oroligofunctional. Preferred are HALS-compounds with one HALS-group anddifunctional organo P-acids, HALS compounds with two or more HALS-groupsand difunctional organo P-acids or HALS-compounds with two or moreHALS-groups and monofunctional organo P-acids. Depending on therequirements, the molar ratio of the HALS-groups and the organo P-acidgroups can be between 1:99 and 99:1, preferably between 40:60 and 60:40,and more preferably between 45:55 and 55:45 and most preferably theratio is equimolar (50:50).

Preferred organo P-acids of formula (II) are C₁-C₁₈alkyl phosphinicacids, di-(C₁-C₁₈ alkyl)phosphinic acids, C₅-C₁₈cycloalkyl phosphinicacids, Di(C₅-C₁₈cycloalkyl) phosphinic acids, C₆-C₁₈aryl phosphinicacids, di-(C₆-C₁₈aryl) phosphinic acids, C₇-C₃₆alkylaryl phosphinicacids, C₇-C₃₆arylalkyl phosphinic acids, di-(C₇-C₃₆alkylaryl) phosphinicacids, di-(C₇-C₃₆arylalkyl) phosphinic acids, C₁-C₁₈alkylenbisphosphinic acids, C₁-C₁₈alkyl phosphonic acids, C₁-C₁₈alkylphosphonic acids monoester, C₅-C₁₈cycloalkyl phosphonic acids,C₅-C₁₈cycloalkyl phosphonic acids monoester, C₆-C₁₈aryl phosphonicacids, C₆-C₁₈aryl phosphonic acids monoester, C₇-C₃₆alkylaryl phosphonicacids, C₇-C₃₆alkylaryl phosphonic acids monoester, C₁-C₁₈alkylen-bisphosphonic acids, acidic phosphate ester of the type (OR₉)—P(O)(OH)₂oder (OR₉)₂—P(O)OH.

More preferred organo P-acids of formula (II) are C₁-C₁₂alkyl phosphinicacids, di-(C₁-C₁₂alkyl) phosphinic acids, C₆-C₁₂cycloalkyl phosphinicacids, di-(C₆-C₁₂cycloalkyl) phosphinic acids, C₆-C₁₂aryl phosphinicacids, di-(C₆-C₁₂aryl) phosphinic acids, C₇-C₁₈alkylaryl phosphinicacids, di-(C₇-C₁₈alkylaryl) phosphinic acids, C₁-C₁₂alkylenbis-phosphinic acids, C₁-C₁₂alkyl phosphonic acids, C₁-C₁₂alkylphosphonic acids monoester, C₆-C₁₂aycloalkyl phosphonic acids,C₆-C₁₂cycloalkyl phosphonic acids monoester, C₆-C₁₂aryl phosphonicacids, C₆-C₁₂aryl phosphonic acids monoester, C₇-C₁₈alkylaryl phosphonicacids, C₇-C₁₈alkylaryl phosphonic acids monoester, C₁-C₁₂alkylenbis-phosphonic acids, acidic phosphate ester of the type (OR₉)—P(O)(OH)₂or (OR₉)₂—P(O)OH.

Especially preferred organo P-acids of formula (II) are methylphosphinic acid, dimethyl phosphinic acid, methyl ethyl phosphinic acid,ethyl phosphinic acid, diethyl phosphinic acid, propyl phosphinic acid,di-propyl phosphinic acid, butyl phosphinic acid, dibutyl phosphinicacid, hexyl phosphinic acid, dihexyl phosphinic acid, octyl phosphinicacid, dioctyl phosphinic acid, cyclohexyl phosphinic acid, dicyclohexylphosphinic acid, phenyl phosphinic acid, diphenyl phosphinic acid, tolylphosphinic acid, ditolyl phosphinic acid, xylyl phosphinic acid, dixylylphosphinic acid, biphenyl phosphinic acid, di-biphenyl phosphinic acid,methylene bis-phosphinic acid, ethylene bis-phosphinic acid,1,2-diethyl-ethylene bis- phosphinic acid, phenylethyl phosphinic acid,di(phenyl-ethyl) phosphinic acid, methyl phosphonic acid, ethylphosphonic acid, methylene di-phosphonic acid, ethylene di- phosphonicacid.

Preferred HALS-compounds of formula (I) are 1,3-Benzoldicarboxamid,N,N′-bis-(2,2,6,6-tetramethyl-4-piperidinyl) (Nylostab® S-EED®),2,2,4,4-Tetramethyl-7-oxa-3,20-diazadispiro[5.1.11.2]heneicosan-21-on(Hostavin® N 20), Poly[[6-[(1,1,3,3-tetramethylbutyl)amino]-1,3,5-trazin-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidinyl)imino]-1,6-hexandiyl-[(2,2,6,6-tetramethyl-4-piperidinyl)imino]],as well the reaction product (Hostavin® N 30) of2,2,4,4-Tetramethyl-7-oxa-3,20-di-azadispiro[5.1.11.2]heneicosan-21-on(Hostavin® N 20) and epichlorohydrin.

The most preferred HALS-compound of formula (I) is1,3-Benzoldicarboxamid-N,N′-bis(2,2,6,6-tetramethyl-4-piperidinyl)(which is commercially available from Clariant as Nylostab® S-EED®).

Examples for HALS-compounds resp. organo P-acids are mentioned in thefollowing list. Each compound from one group (a or b) can be reactedresp. mixed with a compound of the other group (c or d)

a) HALS-compounds with one HALS-group

-   -   fattic acid-(C₁₆-C₁₈)-ester of 2,2,6,6-tetramethyl-piperidinol        (Hostavin® 845)    -   3-Dodecenyl-1-(2,2,6,6-tetramethyl-4-piperidyl)pyrrolidin-2,5-dion        (Sanduvor® 3055)    -   2,2,4,4-Tetramethyl-7-oxa-3,20-diaza-dispiro[5.1.11.2]-heneicosan-21-on        (Hostavin® N 20)    -   2,2,4,4-Tetramethyl-20(β-Myristyl/lauryl-oxycarbonyl)-ethyl-7-oxa-3,20-diaza-dispiro[5.1.11.2]-heneicosan-21-on        (Hostavin® N 24)    -   4-Hydroxy-2,2,6,6-tetramethylpiperidin    -   4-Amino-2,2,6,6-tetramethylpiperidin    -   4-Hydroxy-1,2,2,6,6-pentamethylpiperidin    -   4-Amino-1,2,2,6,6-pentamethylpiperidin    -   4-N-Butyl-amino-2,2,6,6-tetramethylpiperidin    -   N-Hydroxyethyl-4-hydroxy-2,2,6,6-tetramethylpiperidin

b) HALS-compounds with two HALS-groups

-   -   1,3-Benzoldicarboxamid,N;N′-bis(2,2,6,6-tetramethyl-4-piperidinyl)        (Nylostab® S-EED®)

c) Difunctional organo P-acids

-   -   C₁-C₁₈-Alkylene bis-phosphinic acids    -   C₁-C₁₈-Alkylene bis-phosphonic acids

e) Monofunctional organo P-acids

-   -   Diphenylphosphinic acid    -   Phenylphosphinic acid    -   Diethylphosphinic acid    -   Ethylphosphinic acid

Preferred polymers for the application of the products of the inventionare polyamides, like polyamide 6, polyamide 11, polyamide 12, polyamide4.6, polyamide 6.6, polyamide 6.9, polyamide 6.10, polyamide 6.12,polyamide 12.12, and polyester like terephthalic acid/alkyldiol basedpolyester (for example PET, PBT), aliphatic polyester, aromaticpolyester, liquid crystal polyester, polyetherester, and polycarbonatesas well as their blends and copolymers.

Especially preferred polymers are polyamide 4.6, polyamide 6.6,polyamide 6, polyamide 11, Polyamide 12, polyethylenterepthalate (PET),polybutylen-terephthalate (PBT), polycarbonate, their copolymers andblends.

The addition of the products of the invention can either take placebefore or during the preparation of the polymer as well as duringfurther processing steps. The products can be used as solids (powder orblend), as solutions (in inert or reactive solvents), as masterbatch oras a concentrate and, in case of un-decomposed melting compounds, alsoas melt.

Of particular advantage is the addition in a free flowing preparationform, as obtained for example from the melt (drop granulationtechniques, prilling, extrusion, etc.) by compacting (roller compactors,tabletting, briquetting, press granulation, etc.) or by granulationprocesses (spraying, fluidized bed granulation, drum granulation, etc.).These manufactured forms also comprise mixtures of the products of theinvention or mixtures with other polymer additives or colorants known inthe art (blends). Apart of the products of the invention, otheradditives or colorants can be added to the polymer before,simultaneously or afterwards, including also blends containing theproducts of the invention.

Examples of such other additives are lightstabilizers (furtherHALS-compounds, UV-absorbers, excited state quenchers), phosphor- orsulphur based processing stabilizers, antioxidants (phenol- or aminebased), antistatics, nucleating agents, clarifiers, flame retardants,reinforcing materials (e.g. mineral fillers, glass fibers, hollow glassspheres, carbon fibers, nanoscale reinforcing materials (e.g. nanoclays,carbon nanotubes), lubricants, anti block agents, colorants (pigmentsand colorants) etc.

The production and application of the products of the invention areshown in the following examples:

EXAMPLE 1 Synthesis of the Salt from Nylostab® S-EED® andDiphenylphosphinic Acid

74.2 g of diphenylphosphinic acid are added to a suspension of 75.3Nylostab® S-EED® in 250 ml ethanol and stirred at 80° C. for 2 h. Thesolvent is removed under vacuum and the colorless, crystalline presscakeis dried at 80° C. in vacuum.

EXAMPLE 2-3

Application of the invented compound in polyamides

General Processing Recipe

The invented compounds are homogenised together with the polyamidepowder on a Collin single screw extruder at the mentioned temperature ofuse. The current of the extruder motor (equivalent to torque), thepressure at the die, the mass temperature as well as the throughput areregistered at constant machine settings.

A lower motor current and/or an increased throughput are important data,as they directly influence the production costs. A constant pressure atthe die induces a good intake and feeding property and is of importancefor the reproducible preparation of end use articles, as for example,injection molding articles or very uniform fibres. An increased pressurebesides induces less damage of the polyamide through chain destructionduring the process; the added additive contributes in this case to thepolymer stability.

The results of the application obtained are summarised in the followingtable. Process average motor Pressure Throughput Example Compound Conc.Polymer Temperature current [A] [bar] [kg/h] 2 None 0% PA 6.6 270 3.2 ±2.0 4.6 ± 1.3 2.34 3 EXAMPLE 1 0.1%   PA 6.6 270 2.8 ± 0.4 6.6 ± 1.33.46

1. A saltlike reaction product formed by reacting one or more componentsof formulae (Ia) to (Ic),

reaction products of

wherein independently of one another A is —O— or —NR′—, R′ is H,C₁-C₁₈-alkyl or a group selected from the group consisting of

wherein R″ is H, or C₁-C₁₈-alkyl, R′″ is H, an aliphatic,cycloaliphatic, aromatic or heteroaromatic residue, R₁ is C₁-C₁₈-alkyl,or two groups R₁ bound to the same carbon form a C₄-C₈-cycloalkylresidue, R₂ is H, C₁-C₁₈-alkyl, or C₇-C₁₈-alkylaryl, R₃ is H, or an-valent aliphatic, cycloaliphatic, aromatic or heteroaromatic residue,R₄ is C₁-C₁₈-alkyl, —C(O)—C₁-C₁₈-alkyl or -C₁-C₈-alkyl—C(O)O—C₁-C₁₈-alkyl; R₅ is H, C₁-C₁₈-alkyl, C₄-C₁₈-cycloalkyl or twogroups R₅ bound to the same carbon form a C₄-C₁₈-cycloalkyl residue andn is a whole number >0 and one or more organo P-acids of formula (II),

wherein independently of one another R₇ is C₁-C₁₈-alkyl,C₁-C₁₈-alkylene, C₅-C₁₂-cycloalkyl, C₅-C₁₂-cycloalkylene, C₆-C₁₈-aryl,C₆-C₁₈-arylene, C₅-C₁₈-heteroaryl, C₅-C₁₈-heteroarylene,C₆-C₃₆-arylalkyl, C₆-C₃₆-arylalkylene, C₆-C₃₆-alkylaryl orC₆-C₃₆-alkylarylene; R₈ is H, an aliphatic, cycloaliphatic, aromatic orheteroaromatic residue or —OR₉; R₉ is H, an aliphatic, cycloaliphatic,aromatic or heteroaromatic residue m is a whole number >0.
 2. Saltlikereaction product according to claim 1 of the general formula (III)selected from the groups (IIIa) to (IIIc)

wherein A, R₁, R₂, R₃, R₄, R₅, R₇, R₈, n and m are defined as inclaim
 1. 3. Saltlike reaction product according to claim 1 of thegeneral formula (IV)

wherein r is a whole number between 0 and 3, s represents (r+1 )/m andA, R₁, R₂, R₇, R₈ and m are defined as in claim
 1. 4. Saltlike reactionproduct according to claim 1 of the general formula (V)

wherein r is 1 and s represents (r+1 )/m and A, R₂, R₇, R₈ and m aredefined as in claim
 1. 5. Saltlike reaction product according to claim 1wherein the molar ratio of the at least one or more components offormulae (Ia) to (Ic) to the one or more organo P-acids is 1:99 to 99:1.6. Saltlike reaction product according to claim 1, wherein the one ormore components of formulae (Ia) to (Ic) is selected from the groupconsisting of 1,3-Benzol-dicarboxamid,N,N′-bis(2,2,6,6-tetramethyl-4-piperidinyl);2,2,4,4-Tetramethyl-7-oxa-3,20-diazadispiro-[5.1.11.2]heneicosan-21-on;Poly-[[6-[(1,1,3,3-tetramethylbutyl)amino]-1,3,5-triazin-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidinyl)imino]-1,6-hexandiyl-[(2,2,6,6-tetramethyl-4-piperidinyl)imino]]and the reaction product of2,2,4,4-Tetramethyl-7-oxa-3,20-diazadispiro-[5.1.11.2]heneicosan-21-onand epichlorohydrin.
 7. Saltlike reaction product according to claim 1,wherein the one or more organo P-acids of formula (II) is selected fromthe group consisting of diphenylphosphinic acid, phenylphosphinic acid,diethylphosphinic acid, ethylphosphinic acid,ethylene-bis(ethylphosphinic acid) and ethylene-bis(ethylphosphonicacid).
 8. Process for the preparation of a saltlike reaction productcomprising the step of reacting one or more HALS-compounds of generalformula (Ia) to (Ic).

reaction products of

wherein independently of one another A is —O— or —NR′—. R′ is H,C₁-C₁₈-alkyl or a group selected from the group consisting of

wherein R″ is H, or C₁-C₁₈-alkyl, R′″ is H, an aliphatic,cycloaliphatic, aromatic or heteroaromatic residue, R₁ is C₁-C₁₈-alkyl,or two groups R₁ bound to the same carbon form a C₄-C₈-cycloalkylresidue, R₂ is H, C₁-C₁₈-alkyl, or C₇-C₁₈-alkylaryl, R₃ is H, or an-valent aliphatic, cycloaliphatic, aromatic or heteroaromatic residue,R₄ is C₁-C₁₈-alkyl, —C(O)—C₁-C₁₈-alkyl or -C₁-C₈-alkyl—C(O)O—C₁-C₁₈-alkyl; R₅ is H, C₁-C₁₈-alkyl, C₄-C₁₈-cycloalkyl or twogroups R₅ bound to the same carbon form a C₄-C₁₈-cycloalkyl residue andn is a whole number >0 with one or more organo P-acids of formula (II),

wherein independently of one another R₇ is C₁-C₁₈-alkyl,C₁-C₁₈-alkylene, C₅-C₁₂-cycloalkyl, C₅-C₁₂-cycloalkylene, C₆-C₁₈-aryl,C₆-C₁₈-arylene, C₅-C₁₈-heteroaryl, C₅-C₁₈-heteroarylene,C₆-C₃₆-arylalkyl, C₆-C₃₆-arylalkylene, C₆-C₃₆-alkylaryl orC₆-C₃₆-alkylarylene; R₈ is H, an aliphatic, cycloaliphatic, aromatic orheteroaromatic residue or —OR₉; R₉ is H, an aliphatic, cycloaliphatic,aromatic or heteroaromatic residue m is a whole number >0.
 9. Processfor the preparation of a premanufactured mixture, wherein the mixture isformed by the reaction of one or more HALS-compounds of formula (Ia) to(Ic).

reaction products of

wherein independently of one another A is —O— or —NR′—, R′ is H,C₁-C₁₈-alkyl or a group selected from the group consisting of

wherein R″ is H, or C₁-C₁₈-alkyl, R′″ is H, an aliphatic,cycloaliphatic, aromatic or heteroaromatic residue, R₁ is C₁-C₁₈-alkyl,or two groups R₁ bound to the same carbon form a C₄-C₈-cycloalkylresidue, R₂ is H, C₁-C₁₈-alkyl, or C₇-C₁₈-alkylaryl, R₃ is H, or an-valent aliphatic, cycloaliphatic, aromatic or heteroaromatic residue,R₄ is C₁-C₁₈-alkyl, —C(O)—C₁-C₁₈-alkyl or -C₁-C₈-alkyl—C(O)O—C₁-C₁₈-alkyl; R₅ is H, C₁-C₁₈-alkyl, C₄-C₁₈-cycloalkyl or twogroups R₅ bound to the same carbon form a C₄-C₁₈-cycloalkyl residue andn is a whole number >0 and one or more organo P-acids of formula (II)

wherein independently of one another R₇ is C₁-C₁₈-alkyl,C₁-C₁₈-alkylene, C₅-C₁₂-cycloalkyl, C₅-C₁₂-cycloalkylene, C₆-C₁₈-aryl,C₆-C₁₈-arylene, C₅-C₁₈-heteroaryl, C₅-C₁₈-heteroarylene,C₆-C₃₆-arylalkyl, C₆-C₃₆-arylalkylene, C₆-C₃₆-alkylaryl orC₆-C₃₆-alkylarylene; R₈ is H, an aliphatic, cycloaliphatic, aromatic orheteroaromatic residue or —OR₉; R₉ is H, an aliphatic, cycloaliphatic,aromatic or heteroaromatic residue m is a whole number >0 comprising thestep of preparing the mixture, wherein the preparing step includes oneof obtaining the mixture from a melt, compacting the mixture,granulating the mixture or mixing the mixture.
 10. A polymer stabilizercomprising at least one reaction as claimed in claim
 1. 11. Saltlikereaction product according to claim 1, wherein the molar ratio of the atleast one or more components of formulae (Ia) to (Ic) to the one or moreorgano P-acids is 40:60 to 60:40.
 12. Saltlike reaction productaccording to claim 1 wherein the molar ratio of the at least one or morecomponents of formulae (Ia) to (Ic) to the one or more organo P-acids is45:55 to 55:45.
 13. Saltlike reaction product according to claim 1wherein the molar ratio of the at least one or more components offormulae (Ia) to (Ic) to the one or more organo P-acids is 50:50.
 14. Asaltlike reaction product made by the process of claim
 8. 15. Thepolymer stabilizer according to claim 10, Use of saltlike reactionproducts or premanufactured mixtures according to claim 1, wherein thepolymer to be stabilized is a polar polymer.
 16. The polymer stabilizeraccording to claim 10, wherein the polymer to be stabilized is apolyamide or polyester.
 17. The polymer stabilizer according to claim10, wherein the polymer to be stabilized is a polyamide.